Cosmetic composition comprising multifunctionalised poly (alpha olefin-copolymer-maleic anhydride)

ABSTRACT

The present invention relates to cosmetic compositions comprising multiple functionalized maleic anhydride/α-olefin copolymers which have been functionalized with a first reactive —OH or —NH 2  group containing organic compound and subsequently with a second reactive —OH or —NH 2  group containing organic compound, different from the first one. Typical examples are multiple functionalized copolymers in which the first reactive —OH group containing compound is a C 14 -C 28  monoalcohol, or a sitosterol, and the second reactive —OH group containing compound is bis-hydroxypropoxyethyldimethicone or bis-hydroxyethoxypropyldimethicone. The cosmetic compositions are particularly suitable for application to the skin, the lips and keratinous materials.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The present invention relates to cosmetic compositions comprisingmultiple functionalized polyanhydrides. More particularly, it relates tocosmetic compositions comprising multiple functionalized maleicanhydride/α-olefin copolymers.

2. Description of the Prior Art

Maleic anhydride/α-olefin copolymers are well-known in the art. Theyhave been proposed for numerous applications in the cosmetic field.Derivatives of these copolymers have also been described in the art.Thus, for example, U.S. Pat. No. 2,615,845 (Lippincott et al.) describesesters of these copolymers with straight-chain C₁₀-C₁₈ alcohols aslubricating oil additives. Similarly, U.S. Pat. No. 4,151,069 (Rossi)describes esters of maleic anhydride/C₁₈-C₅₀ α-olefin copolymers withC₁₈-C₃₀ linear alcohols as dewaxing aids for lubricating oils. In U.S.Pat. No. 4,548,725 (Bridger) C₄-C₄₀ alkyl esters of maleicanhydride/α-olefin copolymers are described for lowering the cloud pointof a mineral oil.

All of these prior references refer to half—or complete alkyl esters ofthe copolymer, i.e. the derivative contains only an alkyl group asfunctional group.

From a technical leaflet of Chevron Phillips Chemical Company LLC of2005 concerning Polyanhydride Resins a product PA-18 is known which is apolyanhydride resin derived from 1-octadecene and maleic anhydride. Thisproduct and its derivatives are stated to be useful in severalapplications, such as thickening agents, dispersing agents and as waterproofer for personal care products. PA-18 can according to this leafletreact with inter alia amines to form amides or imides, and with alcoholsto form half-esters or diesters.

From U.S. Pat. No. 6,492,455 (Nadolsky) it is Known, that reactionproducts of C₆ and higher α-olefin/maleic anhydride copolymers andpolyfunctionalized amines can be used in cosmetic applications such ashair sprays. In U.S. Pat. No. 6,025,501 (Ulmer, et al.) alkylhalf-esters of maleic anhydride/α-olefin copolymers, optionally withrepeat maleamic acid units or maleimide are described for use inpersonal care products such as hair sprays. In U.S. Pat. No. 6,423,785(Esselborn, et al.) maleic anhydride copolymers with functional amineoxide groups are described as dispersants for pigments. Maleic anhydridecopolymers which have been cross-linked with a cross linking agentcontaining at least two cross linkable groups have been described inU.S. Pat. No. 6,706,817 (Plochocka) for use as bioadhesive hydrogels ininter alia cosmetic delivery systems.

However, in so far as the above prior art describes functionalizedderivatives of maleic anhydride/α-olefin copolymers for use in cosmeticapplications, they are single functionalized derivatives, that is to saythat they contain one or more of the same functional groups. In contrastthereto, the functionalized maleic anhydride/α-olefin copolymers of thepresent invention are multiple functionalized, that is to say that theycontain at least two different functional groups. According to thepresent invention it has been found that reacting a maleicanhydride/α-olefin copolymer with a first reactive —OH or —NH₂ groupcontaining organic functionalizing compound to open part of theanhydride rings and treating the resulting modified copolymer with asecond reactive —OH or —NH₂ group containing organic functionalizingcompound to open all or nearly all of the remaining anhydride rings,said second reactive compound being different from the first reactivecompound, produces a multiple functionalized copolymer with unexpectedcosmetic benefit properties as will be described in more detailhereinafter. “Reactive” means tint the hydroxy- or amine-group iscapable of ring-opening of the anhydride and reacting with acarboxy-group of the anhydride after ring-opening of the anhydride.“Different” means not belonging to the same chemical family.

SUMMARY OF THE INVENTION

Thus, in its broadest aspects, the present invention relates to cosmeticcompositions comprising a multiple functionalized maleicanhydride/α-olefin copolymer which has been multiple functionalized byreacting the maleic anhydride/α-olefin copolymer with a first reactive—OH or —NH₂ group containing organic functionalizing compound andsubsequently with a second, different reactive —OH or —NH₂ groupcontaining organic functionalizing compound.

DETAILED DESCRIPTION OF THE INVENTION

The maleic anhydride/α-olefin copolymers, used in the present inventionare those, well-known in the art. The α-olefins are C₈-C₅₀, preferablyC₁₀-C₂₄ and particularly preferably C₁₈ α-olefins. They are usuallyprepared by reacting approximately equimolar amounts of maleic anhydrideand α-olefin in the presence of a free radical initiator. The number ofrepeat units in the copolymer may vary from 2 to 100, and the numberaverage molecular weight may vary from about 350 to about 600,000. Apreferred maleic anhydride/α-olefin copolymer is a maleicanhydride/1-octadecene copolymer with a molecular weight in the range of20.000 to 50.000.

For brevity's sake, the starting maleic anhydride/α-olefin copolymerwill hereinafter be referred to as MA/O copolymer.

The multiple functionalized MA/O copolymer of the present invention areprepared by reacting the copolymer with a first reactive hydroxy—oramine group containing organic functionalizing compound to open part ofthe anhydride rings, and subsequently with a second, different reactivehydroxy—or amine group containing organic functionalizing compound toopen all or nearly all of the remaining anhydride rings. A great varietyof such compounds can be used as first or second reactive compound, suchas ‘skin active’ compounds such as ceramides, panthenylethyl ether,sterols such as sitosterols, tocopherols; linear/branchedsaturated/unsaturated C₂-C₃₄ alcohols; alkyl amines, alkylhydroxyesters, sorbitol esters, sucrose esters; hydrophilic compounds such asglycerol, its mono and di-esters, polyglycerol, amino acids and theirderivatives, mono and polysaccharides, ethoxylated alcohols; fluorinatedoligomers and polymers; natural compounds capable of UV screening suchas tannins, flavonoids, thymol, caffeic acid esters and vitamin E. Othersuitable compounds can be selected from cosmetic benefit agents,skin-conditioning agents, vitamins, anti-acne-actives, anti-wrinkleagents, sunscreen actives and so on. Care should be taken, of course,that the first and the second reactive compound are different. Mixturesof the above compounds can, of course, also be used as the first or thesecond reactive compound, as long as the mixture of first reactivecompounds is different from the mixture of the second reactivecompounds. Preferred reactive —OH group containing compounds arestraight chain alcohols with 8-30, preferably 14-28 carbon atoms.Another preferred group of reactive —OH group containing compounds arethe sit sterols. Yet another preferred group of reactive —OH groupcontaining compounds are hydroxy-terminated silicones such as thesiliconols. Examples of the latter arebis-hydroxyethoxypropyldimethicone andbis-hydroxypropoxyethyldimethicone. Preferred reactive —NH₂ groupcontaining compounds are primary amines. A typical example of a multiplefunctionalized MA/O copolymer of the invention is one wherein the firstreactive compound is a C₁₄ or a C₂₈ straight chain alcohol and thesecond reactive compound is a siliconol as exemplified above.

The reaction of the MA/O copolymer with the first reactive hydroxy—oramine group containing organic compound to open part of the anhydriderings can be carried out in a manner, known per se, e.g. as described inU.S. Pat. No. 3,531,440 or U.S. Pat. No. 2,615,845. By varying thereaction temperature, reaction time, catalyst and relative molar amountsof reactants the number of opened rings and functionalizing groupsformed can be controlled. In general, from 5 to 90%, usually from 20% to80%, preferably from 30 to 70%, and particularly preferably 50% of theavailable anhydride rings should be opened in this way The resultingreaction product, which contains, apart from the functionalizing groups,still unopened anhydride rings is hereinafter for brevity's sakereferred to as “modified MA/O copolymer”

The thus obtained modified MA/O copolymer is treated with the second,different reactive hydroxy—or amine group containing organic compound.This second different reactive compound can be selected from the variousmaterials indicated above. Typical examples of preferred materials aresiliconols, silanols, hydroxy-terminated polydialkylsiloxanes,dimethiconol, dimethicone (co)polyols, alkoxylated silanols etc., andmixtures of these compounds. Preferred second reactive hydroxy-groupcontaining organic compounds are bis-hydroxypropoxyethyldimethicone andbis-hydroxyethoxypropyldimethicone. All or nearly all of the remainingunopened anhydride rings in the modified MA/O copolymer will be openedby the reaction with the second, different reactive organic compound andconverted into functionalizing groups. By judicious choice of theamounts of reactants, temperature, catalyst and reaction time the degreeof ring-opening can be controlled. In general from 95% to 10%, usuallyfrom 80% to 20%, preferably from 70% to 30% and particularly preferably50% of the total number of originally present anhydride rings in themaleic anhydride/α-olefin copolymer will be opened by the secondreactive organic compound. It is to be noted that if the first and/orthe second functionalizing reactive agent is bi-functional, e.g. such asthe above-mentioned dimethicone derivatives, some crosslinking may occurin the multiple functionalized MA/O copolymers.

If not all of the anhydride rings are opened with the above two types offunctionalizing reactive agents, any remaining anhydride rings may, ifdesired, be opened by reacting them with a third reactive —OH or —NH₂group containing organic compound, different from the one(s), used inthe first and second step. A typical example of such a third reactiveagent is ethanol.

Any free carboxy groups in the resulting finally obtained multiplefunctionalized maleic anhydride/α-olefin copolymer may remainunmodified, or they may be converted into salts such as the alkalimetal, ammonium and substituted ammonium salts, or into esters or amidesin manners, known per se. Preferably the carboxy groups remain free, inorder to obtain optimum skin-substantivity of the multiplefunctionalized copolymers. The multiple functionalized copolymers of theinvention will have a molecular weight of between 500 and 1,000,000,depending of course on the type of reactive agents used in theirpreparation.

The multiple functionalized copolymers of the present invention areuseful for use in cosmetic compositions. They are skin-substantive, andcan deliver particular cosmetic benefit agents and skin-actives to theskin. They can impart certain benefits to the compositions, e.g. pigmentwetting, act as binders in compressed powder compositions, andparticularly in solid and liquid compositions, they can act as improvedfilm-forming agents and improved dispersants for pigments in a lipidphase. They can be used in mascara products, foundations, creams,lotions, sunscreen and suntan products, blush formulations, make-upproducts, eye shadows, and so. They are particularly useful in cosmeticproducts for the lips, such as lipsticks and fluid lip products fordelivering an improved gloss and comfort and long-lasting wearproperties without transferability. A multiple functionalized copolymer,prepared with a C₂₈-monoalcohol and a siliconol is particularly suitablefor use in lipsticks, while a multiple functionalized copolymer,prepared with a C₁₄-monoalcohol and a siliconol is very suitable for usein fluid lip products.

The cosmetic compositions of the present invention comprise the multiplefunctionalized copolymer of the invention in an amount of 0.5-75%,preferably 0.75-35% and particularly preferably 1.0-20% by weight of thefinal composition.

The cosmetic compositions comprising the multiple functionalizedcopolymers can contain all the usual ingredients, commonly used in suchcompositions, such as resins, (co)polymers, silicones, volatilecarriers, hydrocarbons, pigments, excipients such as talc, mica,silicas, titanium dioxide, zinc oxide, nylon particles, kaolin, calciumcarbonate, starch, antioxidants, vegetable and mineral oils and fats,clays, conditioning agents, waxes, pearlescent agents, flavours,perfumes, vitamins, sunscreen agents, emollients, emulsifiers, skin careagents, surfactants, bactericides, preservatives and so on. With some ofthe above ingredients such as particulate excipients and pigments, themultiple functionalized copolymers of the present invention can be“linked”, thus increasing their wetting and dispersion in a lipid phase.The multiple functionalized copolymers of the invention are also quitesuitable as coating agents for particulate materials such as powders,particulate pigments and other cosmetic ingredients in particle form.

All such suitable ingredients can be found in reference books such asthe CTFA Cosmetic Ingredient Handbook, second Edition, The Cosmetic,Toiletries and Fragrance Association, Inc, 1988, 1992.

The invention will now further be illustrated by way of Examples. Allpercentages are by weight, unless otherwise indicated

EXAMPLE 1 Cross-Linked Silicone-Polyester C₁₄ Functionalized MA/OCopolymer.

1A 1B % % PHASE “A” ISODODECANE 64.10 16.10 OCTADECENE/MA COPOLYMER16.30 39.10 MYRISTYL ALCOHOL 8.00 19.20 PHASE “B” WATER 1.30 1.30 CITRICACID 0.30 0.30 PHASE “C” DIMETHYL SILOXANE, 10.00 24.00HYDROXYALKYL-TERMINATED

The copolymer was dissolved in isododecane at about 120° C. To thedispersion, myristyl alcohol was added and the mixture was allowed toreact for 4 hours. To the resulting Phase A Phase B was then added andfinally to complete the reaction hydroxyalkyl terminated dimethylsiloxane (Phase C) was added while heating for 1 hour at 110° C. Thetemperature was stabilized at 80° C. at which temperature the whole masswas kept for a further 12 hours. A dispersion of a silicone-C₁₄polyester multiple functionalized MA/O copolymer in isododecane wasobtained.

The degree of substitution in the multiple functionalized MA/O copolymerwas in Phase A 79.9%, and in Phase C 19.2%, the total degree ofsubstitution being 99.1%

EXAMPLE 2 Cross-Linked Silicone-Polyester C₁₆ Functionalized MA/OCopolymer.

% PHASE “A” ISODODECANE 38.40 OCTADECENE/MA COPOLYMER 16.30 CETYLALCOHOL 6.50 PHYTOSPHINGOSINE 0.20 PHASE “B” WATER 1.30 CITRIC ACID 0.30PHASE “C” CYCLOPENTASILOXANE 27.00 DIMETHYL SILOXANE, 10.00HYDROXYALKYL-TERMINATED

The copolymer was dissolved in isododecane at about 120° C. To thedispersion, cetyl alcohol and phytosphingosine were added and themixture (Phase A) was allowed to react for 4 hours. Phase B was thenadded and finally to complete the reaction hydroxyalkyl terminateddimethyl siloxane was added while heating for 1 hour at 110° C. Thetemperature was stabilized at 80° C. at which temperature the whole masswas kept for a further 12 hours. A dispersion of a silicone-C₁₆ multiplefunctionalized polyester MA/O copolymer in isododecane andcyclopentasiloxane was obtained.

The degrees of substitution were in Phase A 58.8% and in Phase C 19.2%,the total degree of substitution being 78.0%.

EXAMPLE 3 Cross-Linked Silicone-Polyester C₁₈ Functionalized MA/OCopolymer

% PHASE “A” ISODODECANE 63.90 OCTADECENE/MA COPOLYMER 18.00DODECYLHEXADECANOL 5.30 PHYTOSPHINGOSINE 0.20 PHASE “B” WATER 1.30CITRIC ACID 0.30 PHASE “C” DIMETHYL SILOXANE, 11.00HYDROXYALKYL-TERMINATED

The copolymer was dissolved in isododecane at about 120° C. To thedispersion, dodecylhexadecanol and phytosphingosine were added and themixture (Phase A) was allowed to react for 4 hours. Then Phase B wasadded and finally to complete the reaction hydroxyalkyl terminateddimethyl siloxane was added while heating for 1 hour at 110° C. Thetemperature was stabilized at 80° C. at which temperature the whole masswas kept for a further 12 hours. A dispersion of a silicone-C₁₈polyester multiple functionalized MA/O copolymer in isododecane wasobtained.

The degrees of substitution were in Phase A 23.2% and in Phase C 19.1%,the total degree of substitution being 42.3%.

EXAMPLE 4 Cross-Linked Silicone-Polyester C₁₄-C₁₈ Functionalized MA/OCopolymer

% PHASE “A” ISODODECANE 63.50 OCTADECENE/MA COPOLYMER 17.50 HEXYLDECANOL4.80 MYRISTYL ALCOHOL 4.80 PHYTOSPHINGOSINE 0.30 PHASE “B” WATER 1.30CITRIC ACID 0.30 PHASE “C” DIMETHYL SILOXANE, 7.50HYDROXYALKYL-TERMINATED

The copolymer was dissolved in isododecane at about 120° C. To thedispersion, hexyldecanol and phytosphingosine were added and theresulting mixture (Phase A) was allowed to react for 4 hours. Phase Bwas then added and finally to complete the reaction hydroxyalkylterminated dimethyl siloxane was added while heating for 1 hour at 110°C. The temperature was stabilized at 80° C. at which temperature thewhole mass was kept for a further 12 hours. A dispersion of asilicone-C₁₄-C₁₈ polyester multiple functionalized MA/O copolymer inisododecane was obtained.

The degrees of substitution were in Phase A 86.4% and in Phase C 13.4%,the total degree of substitution being 99.8%.

EXAMPLE 5 Beta-Sitosterol-Branched Polyester C₁₈-C₂₀ Functionalized MA/OCopolymer.

% PHASE “A” TRIMETHYLOLPROPANE- 76.00 TRIISOSTEARATE OCTADECENE/MACOPOLYMER 8.50 BETA SITOSTEROL 4.30 PHASE “B” OCTYLDODECANOL 11.20

The copolymer was dissolved in trimethylolpropane-triisostearate atabout 120° C. To the dispersion, betasitosterol was added and themixture (Phase A) was allowed to react for 4 hours. Phase B was thenadded to complete the reaction under heating for 1 hour at 110° C. Thetemperature was stabilized at 80° C. and the whole mass was kept at thistemperature for a further 12 hours. A dispersion of a betasitosterol-branched C₁₈-C₂₀ polyester multiple functionalized MA/Ocopolymer in trimethylolpropane-triisostearate was obtained.

The degrees of substitution were in Phase A 21.3% and in Phase B 77.2%,the total degree of substitution being 98.5%.

EXAMPLE 6 Cross-Linked Silicone-Beta Sitosterol Functionalized MA/OCopolymer

% PHASE “A” ISODODECANE 58.50 OCTADECENE/MA COPOLYMER 18.00 BETASITOSTEROL 7.70 PHASE “B” WATER 1.30 CITRIC ACID 0.30 PHASE “C” DIMETHYLSILOXANE, 14.20 HYDROXYALKYL-TERMINATED

The copolymer was dissolved in isododecane at about 120° C. To thedispersion, beta-sitosterol was added and the mixture (Phase A) wasallowed to react for 4 hours. Phase B was then added and finally tocomplete the reaction hydroxyalkyl terminated dimethyl siloxane wasadded while heating for 1 hour at 110° C. The temperature was stabilizedat 80° C. at which temperature the whole mass was kept for a further 12hours. A dispersion of a silicone-beta sitosterol multiplefunctionalized MA/O copolymer in isododecane was obtained.

The degrees of substitution were in Phase A 36.1% and in Phase C 24.7%,the total degree of substitution being 60.8%.

EXAMPLE 7 Coating of Pigments with the Functionalized Copolymer ofExample 5

COMPONENTS % PHASE “A” PIGMENTS (Talc-Mica-Iron oxide) 82.00 PHASE “B”Functionalized copolymer of Example 5  8.00 ISODODECANE 10.00

Under strong turbulence Phase B was sprayed onto the pigments (Phase A).The solvent (isododecane) was then removed by drying the mixture in anoven at 80° C. for 12-24 hours.

EXAMPLE 8 Functionalized Copolymer (from Example 1) Containing CosmeticComposition

(Lip Shine Fluid)

COMPONENTS % % Functionalized copolymer 92.50  92.50 (1) (2) ETHYLALCOHOL 1.50 PIGMENTS 5.00 WATER 1.00 (1) from Example 1A (2) fromExample 1B

EXAMPLE 9 Functionalized Copolymer (from Example 1) Containing CosmeticComposition

(Lip Shine Stylo)

COMPONENTS % CYCLOPENTASELOXANE 32.00 POLYETHYLENE 7.00 functionalizedcopolymer of Example 1 52.00 ETHYL ALCOHOL 2.00 PIGMENTS 5.00 MICA 2.00

EXAMPLE 10 Functionalized Copolymer (from Example 3) Containing CosmeticComposition

(Mascara)

COMPONENTS % PHASE “A” WATER 39.70  GLYCERIN 2.00 HYDROXYETHYLCELLULOSE2.00 ACACIA SENEGAL GUM 6.00 PHASE “B” IRON OXIDE 9.00 PHASE “C”HYDROGENATED RAPESEED OIL 4.00 GLYCERYLSTEARATE 3.00 CETEARYL GLUCOSIDEAND 4.00 CETEARYL ALCOHOL functionalized copolymer of Example 3 30.00 PHASE “D” PRESERVATIVE 0.30

EXAMPLE 11 Functionalized Copolymer (from Example 5) Containing CosmeticComposition

(Eye Shadow Compact Powder)

COMPONENTS % TALC 41.50 MICA 15.00 IRON OXIDE 25.00 NYLON 12 6.00functionalized copolymer of Example 5 12.00 PRESERVATIVES 0.50

EXAMPLE 12 Functionalized Copolymer Coated Pigments (from Example 7)Containing Cosmetic Composition

(Eye Shadow)

COMPONENTS % Coated pigments of Example 7 90.50 NYLON 12 6.00functionalized copolymer of Example 5 3.00 PRESERVATIVES 0.50

1. A cosmetic composition comprising, in addition to conventionalcosmetic ingredients, from 0.5-75% by weight of the composition of amultiple functionalized maleic anhydride/C₈-C₅₀ α-olefin copolymer,obtainable by reacting a maleic anhydride/C₈-C₅₀ α-olefin copolymerhaving a molecular weight of between 350 and 600,000 with a firstreactive —OH or —NH₂ group containing organic functionalizing compoundto open from 5% to 90% of the anhydride rings and reacting the resultingmodified copolymer with a second reactive —OH or —NH₂ group containingorganic functionalizing compound to open from 95% to 10% of theanhydride rings, said second reactive functionalizing compound beingdifferent from the first reactive functionalizing compound, saidmultiple functionalized copolymer having a molecular weight of between500 and 1,000,000, wherein said first or said second reactive —OH groupcontaining organic functionalizing compound is selected from the groupconsisting of straight chain alcohols with 8-30 carbon atoms,sitosterols and hydroxy terminated silicones.
 2. The cosmeticcomposition according to claim 1, wherein any remaining anhydride ringsin the multiple functionalized copolymer is opened by reaction with athird reactive —OH or —NH₂ group containing organic compound, said thirdreactive compound being different from the first and the second reactive—OH or —NH₂ group containing organic functionalizing compound.
 3. Thecosmetic composition according to claim 1 or 2, wherein the multiplefunctionalized copolymer contains an α-olefin containing from 10-24carbon atoms.
 4. The cosmetic composition according to claim 3, in whichthe α-olefin contains 18 carbon atoms.
 5. (canceled)
 6. The cosmeticcomposition according to claim 1, in which the alcohol is a straightchain monoalcohol with 14-28 carbon atoms 7.-8. (canceled)
 9. Thecosmetic composition according to claim 1, in which the second reactiveorganic functionalizing compound is a siliconol.
 10. The cosmeticcomposition according to claim 9, in which the siliconol isbis-hydroxypropoxyethyldimethicone orbis-hydroxyethoxypropyldimethicone. 11.-14. (canceled)
 15. A method forimproving the gloss or long-lasting wear property of a lipstick or fluidlip product on the lip comprising applying to the lip a lipstick orfluid lip product comprising a cosmetic composition according to claim1, claim 2, claim 3, claim 4, claim 6, claim 9 or claim
 10. 16. A methodof coating a particulate cosmetic ingredient comprising spraying amultiple functionalized copolymer according to claim 1, claim 2, claim3, claim 4, claim 6, claim 9 or claim 10 onto the particulate cosmeticingredients.